US5416134A - Water-borne acrylic emulsion pressure sensitive latex adhesive composition - Google Patents
Water-borne acrylic emulsion pressure sensitive latex adhesive composition Download PDFInfo
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- US5416134A US5416134A US08/171,196 US17119693A US5416134A US 5416134 A US5416134 A US 5416134A US 17119693 A US17119693 A US 17119693A US 5416134 A US5416134 A US 5416134A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Definitions
- the present invention relates to pressure sensitive adhesives and more particularly to a water-based pressure sensitive adhesive suitable for high performance applications.
- pressure sensitive adhesive tapes are being shifted from organic solvent systems to aqueous latices in order to reduce air pollution and fire hazard, as well as eliminate the rising expense of organic solvents.
- Pressure sensitive adhesives for high performance application must meet or exceed diverse, often seemingly incompatible, criteria. Initially, the adhesive must coat well on silicone or other release sheets. The adhesive also must exhibit tenacious adherence to film face stock which may serve a masking function or may convey information, e.g. by its imprinting.
- the adhesive coated film face stock When the adhesive coated film face stock is removed from the release sheet, the adhesive must exhibit initial tack and peel performance when pressure-applied to a substrate.
- the substrate beating the adhesively-bound film face stock may be subjected to a variety of manufacturing operations over time. Thermal cycling of the substrate is a condition to which high performance, pressure sensitive adhesives must be designed to confront.
- removal When the film face stock is removed from the substrate, removal must be clean, i.e. no visible trace of the adhesive should remain on the substrate.
- Heat aging of the film face stock/substrate laminate tends to cause the adhesive to "build", that is, the necessity to utilize excessive force to remove the film face stock.
- the adhesive should stick well initially, but not so well that its later removal is difficult. Then too, the adhesive must possess shelf life, viscosity, etc. making it compatible with existing coating and handling techniques utilized in the art.
- 24491/84 proposes pressure sensitive adhesives comprising an acrylic copolymer synthesized from 2-ethylhexyl acrylate and n-butyl acrylate, acrylonitrile, acrylic acid, N-methylol acrylamide, and optionally vinyl sulfonic acid; and plasticizer.
- U.S. Pat. No. 4,540,739 proposes a pressure sensitive adhesive (PSA) having improved shear properties and comprising a latex of a polymer having a T g which is less than about 0° C. and formed by emulsion polymerizing a monomeric mixture of 60-99.5 wt-% of a C 1-C 8 alkyl or alkanol ester of (meth)acrylic acid and from about 0.5 to about 40 wt-% of a C 3 -C 9 ethylenically unsaturated acid.
- PSA pressure sensitive adhesive
- the monomeric mixture can include up to 5 wt-% of an amide of a C 3 -C 9 ethylenically unsaturated acid which amide may be unsubstituted or substituted at the nitrogen atom by a C 1 -C 8 alkyl or alkanol radical.
- the PSA has its pH adjusted to be equal to or greater than about 6 with an agent selected from hydroxides and salts of lithium, sodium, potassium, and mixtures thereof.
- the present invention is directed to an aqueous emulsion acrylic pressure sensitive adhesive composition that excels in high performance application.
- the inventive adhesive composition comprises in water:
- At least one of (A)(a) or (A)(b) is an aqueous emulsion copolymer made by emulsion polymerization and at least one of (B)(a) or (B)(b) is an aqueous emulsion copolymer made by emulsion polymerization;
- the emulsion copolymer(s) includes up to 25% by weight of styrene or other aromatic monomer(s).
- the novel adhesive composition is substantially-free of cross-linking monomers, copolymerizable emulsifiers, N-methylol acrylamides and the like, cross-linking additives (i.e. post-polymerization addition yielding a cross-linking reaction or formation of interpolymer bonds, such as, for example, zinc salts, diisocyanates, diglycidyl compounds, etc.), and zwitterionic monomers (i.e. not more than about 15 wt-% of cross-linking ingredient, including monomers and additives). Basification of the ethylenically-unsaturated carboxylic acid copolymer(s) results in a self-thickening adhesive composition and contributes to manufacturing reproducibility of the adhesive composition.
- cross-linking additives i.e. post-polymerization addition yielding a cross-linking reaction or formation of interpolymer bonds, such as, for example, zinc salts, diisocyanates, diglycidyl compounds, etc
- Advantages of the present invention include a manufacturing process that enables the reproducible production of the novel adhesive composition. Another advantage is the ability to synthesize an adhesive composition base that is compatible and blendable with other conventional ingredients at all levels. A further advantage is the ability to produce an ultra-removable adhesive composition. A yet further advantage is the ability to formulate adhesive compositions of varying desired performance levels by blending of the acrylic acid copolymer and the acrylamide copolymer at different ratios.
- the major ingredient in the emulsion copolymer(s) broadly is a C 4 -C 18 alkyl (meth)acrylate monomer and advantageously a C 4 -C 12 alkyl (meth)acrylate monomer.
- n-Butyl acrylate and 2-ethylhexyl acrylate are two monomers that have proven advantageous in forming the emulsion copolymer(s) of the present invention, though other straight chain, alicyclic, and cyclic alkyl (meth)acrylate monomers may be used as is necessary, desirable, or convenient.
- the parentheticals used herein designate optional content, i.e.
- (meth)acrylate means "acrylate” or "methacrylate”, and the same is true for the parenthetical plurals used herein. Also by convention, copolymer and interpolymer both mean a polymer of two or more monomers. The selection of the terms as used herein is for the clarity of understanding and not by way of limitation.
- a combination of acrylamide and ethylenically unsaturated carboxylic acid form the balance of the emulsion copolymer(s) and their combination is important to the high performance properties realized.
- the proportion of acrylamide ranges from about 0.1 wt-% to about 5 wt-% while the proportion of unsaturated acid ranges from about 0.2 to about 10% by weight.
- the acrylamide content includes N-alkyl and other substituted acrylamides and polyamides, e.g. diamides.
- Cross-linking monomers, e.g. N-methylol acrylamides, may be present in minor amount (e.g.
- Latent cross-linking functionality tends to lower tack and initial peel values, thus reducing the strength and suitability of the adhesive composition for some applications.
- N-methylol substituted acrylamides may be present in the formulation, but such components generate formaldehyde when the films are coated which is a health concern in the industry.
- Latent cross-linking functionality additionally can cause a loss of adhesive properties of aged unapplied films and labels.
- Additive cross-linkers cause problems in use with adhesive batch-to-batch consistency, pot life, reactivity, and variation in adhesive performance. Fortuitously, latent cross-linking functionality and additive cross-linkers are not required of the novel adhesive composition.
- Additional acids include, for example, butenic acids, e.g. crotonic acid, isocrotonic acid, and vinyl acetic acid; an acid from the fumaric acid series, e.g. fumaric acid, maleic acid, glutaconic acid, allyl malonic acid, and allyl succinic acid; and dicarboxylic acids, e.g. itaconic acid.
- Lower alkyl-substituted (e.g. C 1 -C 4 alkyl group) acrylic acid e.g.
- methacrylic acid additionally can find use in formulating the emulsion copolymer(s) of the present invention.
- ratio of acrylamide to acrylic acid broadly ranges from about 1:10 to about 10:1 by weight with about 1:2 being optimum for acrylamide to acrylic acid. This ratio is believed to be important in providing removability characteristics with retention of good initial tack and peel values.
- one or both of the emulsion copolymers or the IPN can contain styrene or other aromatic polymerizable monomer, vinyl chloride, vinylidene chloride, or other hydrophobic monomer ethylene vinyl acetate.
- Styrene can be present in an amount up to about 25% by weight of both copolymers or IPN and preferably about 5% by weight styrene is included in the monomer mixture(s) that is subjected to emulsion copolymerization in accordance with the precepts of the present invention.
- a blend of copolymers with separate acrylamide and unsaturated acid is used in formulating the novel adhesive composition, then at least one of the copolymers is made by emulsion polymerization techniques, while the other copolymer can be made by emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or other technique [see generally, D. H. Solomon, The Chemistry of Organic Film Formers, Robert E. Krieger Publishing Company, Huntington, N. Y. (1977)].
- the interpenetrating polymer network can be based either on the acrylamide-containing copolymer or on the unsaturated acid-containing copolymer, though synthesis again is by emulsion polymerization. Details on synthesis of interpenetrating polymer network emulsions can be found in U.S. Pat. No. 4,616,057, the disclosure of which is expressly incorporated herein by reference.
- the emulsion copolymers or IPN can be made by a batch, semi-batch, or continuous process, though preferably a semi-batch process is employed. Despite the ability to meter a constant mixture of the monomers to the reaction vessel, the product emulsion copolymer blend evidences a two-stage morphology, as will be explored further below.
- Emulsion polymerization in the aqueous continuous phase is conducted in conventional fashion, such as described by D. H. Solomon in The Chemistry of Organic Film Formers, pp 294-303, supra.
- a conventional emulsifier e.g. sodium alkylaryl polyethoxy sulfonate or the like, is utilized during the emulsion polymerization reaction.
- the copolymerization with acrylic acid preferably is run without a buffer at a pH of about 2-3 as determined by the decomposition of the persulfate catalyst (i.e. sulfonic acid generation). Since the pKa of acrylic acid is about 4, the pH of this emulsion reaction mixture should be very low, e.g. much less than 4, so that the acrylic acid copolymer does not ionize and thicken during the reaction.
- this copolymer can be basified (i.e. the pH raised with base above pH of reaction) to a pH of above 3, broadly 3-10, and preferably about 8-9. Basification provides a self-thickening adhesive composition and has been determined to enable manufacturing reproducibility of the adhesive composition.
- aqueous ammonia can be used to basify the composition, though other bases, e.g. various amines, imines, alkali metal and alkaline earth metal hydroxides, carbonates, etc., can be used as is necessary, desirable, or convenient.
- bases e.g. various amines, imines, alkali metal and alkaline earth metal hydroxides, carbonates, etc.
- the emulsion copolymers or IPN need not contain any cross-linking monomers, N-methylol acrylamides, or zwitterionic monomers. These ingredients generally lower tack and initial peel values, thus reducing the strength and suitability of the adhesive contact, especially in high performance applications. Latent cross-linking functionality, additionally, can cause a loss of adhesive properties for aged unapplied films and labels and yellowing or discoloration of the adhesive. Thus, while such ingredients can be included in the emulsion copolymers or IPN in minor amount (e.g. not more than about 15 wt-%), they are not necessary and desirably are avoided.
- the next ingredient utilized in formulating the novel adhesive composition is a surfactant (preferably a phosphate ester surfactant) that should be present in a proportion of about 0.01% to 10% by dry weight of the emulsion copolymers or IPN.
- a surfactant preferably a phosphate ester surfactant
- the phosphate ester surfactant serves a dual function in the adhesive composition. One function is to promote the removability of a label or other substrate coated with a cured residue of the adhesive composition. The second function is the ability of the phosphate surfactant to wet-out silicone release sheets which enhances coatability of the aqueous emulsion polymer on such release sheets. Too much phosphate, however, tends to promote foaming of the adhesive composition which detracts from its use in commercial settings.
- phosphate emulsifiers include, for example, ammonium, potassium or sodium salts of alkyl aryl polyethoxy phosphates, alkyl ethoxy phosphates, alkyl phosphates, alkyl polyethoxy phosphates, and the like, and even mixtures thereof.
- the phosphate coester structure augments the removability and other performance characteristics.
- Carboxyl and amide-containing acrylate polymers may be expected to contain interpolymer hydrogen bond interactions including COOH/CONH 2 , COOH/COOH, and CONH 2 /CONH 2 . These interpolymer associations are believed to contribute to the removable adhesive properties of the novel adhesive composition. This relationship between polymer structure and performance also is supported by the observation that completion of the reactions at lower non-volatile (nv) solids in combination with consuming unreacting monomers results in a different performance profile for the copolymer blend or IPN. Heat aged performance of different nv solids emulsion copolymer blend-based adhesive compositions suggest polymer structures that develop during the polymerization and that this improves adhesive removability. It is believed that polymer hydrophilic morphology develops during the latter states of reaction to create an amide rich latex shell.
- Typical phosphate coester surfactants contain hydrophobic groups and a --POOH moiety.
- Commercial synthetic phosphate surfactants are functionally similar to phospholipids and are capable of hydrophobic, hydrogen bonding, and electrostatic interactions.
- the strong effects observed for blending small amounts of phosphate surfactants on emulsion viscosity's and polymer film adhesion performance indicates a strong association between phosphate surfactant and latex particles.
- the structures of the carboxylate and amide copolymers or the structure of the IPN in combination with the phosphate surfactant also should influence the character of adhesive substrate interfaces.
- Phosphate hydrogen bonding or electrostatic interaction is possible with carboxyl and amide polymer groups. Phosphate-polymer associations could form a colloid interpolymer network.
- a postulated colloid polymer structure involves an acrylate polymer core surrounded by a carboxyl/amide rich polymer shell.
- the surface of the latex is composed of the phosphate ester surfactant and the emulsion copolymer emulsifier.
- the anionic groups of the surfactant and emulsifier support an electrical charged layer around the particle providing colloid stability. Ionization of polymer bound carboxylic acid at, e.g., pH 3-6, expands the outer layers of the latex particle, resulting in increased latex viscosity.
- Film formation is affected by the outer layer of structure of the colloid IPN polymer or polymer blend during particle coalescence. The structural changes affect film adhesive properties.
- Polymer film structure is affected by phosphate coester hydrophobe structure and the extent of ionization of the carboxylic functionality. These interfacial phenomena result in specific structural networks in the coalesced latex adhesive film. This film structure, in turn, yields special performance properties (i.e. low peel build on aging) having pronounced effects on peel and shear values.
- Other surfactants e.g. polyoxyethylene-polyoxypropylene block copolymers, alkanol amides, amine oxides, amines, ethoxylated amines, imidazolines, etc.
- surfactants e.g. polyoxyethylene-polyoxypropylene block copolymers, alkanol amides, amine oxides, amines, ethoxylated amines, imidazolines, etc.
- the adhesive is removable from a variety of substrates cleanly, i.e. no visible residue, including, for example, metals (e.g., stainless steel, aluminum, etc.) and plastics (e.g., polyethylene, polypropylene, polystyrene, polycarbonate, ABS resin, PVC resin, etc.)
- metals e.g., stainless steel, aluminum, etc.
- plastics e.g., polyethylene, polypropylene, polystyrene, polycarbonate, ABS resin, PVC resin, etc.
- Build on aging generally is less than 100% when the applied adhesive is maintained at 70° C. for three weeks and less than 50% when aged at room temperature for three weeks.
- a viscosity of about 1,000-10,000 centipoises is compatible with existing equipment and handling procedures, and preferably a viscosity of about 2,000-4,000 centipoises is maintained.
- the adhesive composition may be incorporated into the adhesive composition, including, for example, wetting agents, pigments, opacifying agents, anti-foam agents, and the like and mixtures thereof.
- the adhesives may be applied to one or both sides of the film face stock in a conventional manner, for example, by spraying, knife coating, roller coating, casting, drum coating, dipping, and the like. Indirect application using a transfer process with silicon release paper also can be used. After the adhesive has been applied, the coated film face stock is dried conventionally.
- Emulsion polymerizations were conducted in a 3-liter Pyrex brand glass reactor equipped with water bath, mechanical stirrer, N 2 atmosphere, condenser, thermocouple, and pumps for monomer and initiator feeds.
- a monomer emulsion was prepared with 800 g total monomer (the amount used in all preparations), deionized water (196.3 g), and Triton X-200 emulsifier.
- the reactor was charged with deionized water (230 g) and the initial monomer emulsion (21.3 g, 2.0%) and warmed to 76° C. initiation temperature with stirring. Catalyst #1 and 2 wt-% of catalyst #2 were used to initiate the reaction. After the initiation reaction, the remaining monomer emulsion and potassium persulfate solution were delayed fed at a constant rate over a 3 hour time period while maintaining a reaction temperature of 80° C. The reaction temperature was maintained for an additional 30 minutes after the feed ended.
- reaction temperature then was lowered to 50° C. and chaser catalysts, tert-butyl hydroperoxide (70%) aqueous solution (0.4 g in 10 ml) and sodium formaldehyde sulfoxylate aqueous solution (0.4 g in 10 ml), were added to reduce residual monomer content.
- the reaction temperature of 50° C. was maintained for 30 minutes and then lowered to 35° C., and a biostat (Kathon LX, 1.5%, 2 g) was added.
- Emulsion copolymer 4886-155 had a solids content of 61%, a pH of 2.6, and viscosity of 3,040 cps (Brookfield RV spindle #4 at 20 rpm).
- Polyken Tack Test This test is conducted on a Polyken, Jr. Probe Tack Tester (Polyken is a trademark of the Kendall Company) supplied by Testing Machines, Inc. (Amityville, N.Y.) under the following conditions:
- Probe 304 SS. 0.5 cm. diameter probe polished to 4/0 emery paper finish.
- Annular Weight 20 gm.-100 gm/cm2 pressure of a 0.5 cm. diameter probe
- Emulsion polymer physical blend of a carboxylated acrylic latex and an amide functional acrylic latex 1.
- Interpenetrating emulsion polymer networks containing carboxylic and amide functionalities.
- the emulsions were all compounded with phosphate coester surfactant and basified with aqueous ammonia to afford pressure sensitive adhesives. This compounding is summarized in Table 3 below.
- Polymer architecture 1 is a comparative formulation. Adhesives prepared from this polymer system with copolymerization of 1 wt-% acrylamide and 2 wt-% acrylic acid typically exhibit 0.5 to 1.0 lbs/in of initial peel, building to about 1.5 lbs/in of peel after aging at 70° C. Loop tacks are about 1.0 lbs/in. This is the performance reference for the other polymers.
- the emulsion polymer blend adhesive exhibited the higher initial peel values of the carboxylated latex and the lower heat-aged peel build of the acrylamide latex. These results indicate higher performing water-borne acrylic emulsion pressure sensitive adhesives can be prepared with latex blends. Also, latex blend ratios may provide specific control over removable adhesive performance. This latter feature would permit greater formulation latitude in developing specialty adhesives.
- a carboxylated acrylate emulsion copolymer was compounded with a polyacrylamide solution polymer to afford adhesive 5121-17.
- This adhesive displayed similar initial peel values, but lower peel values after heat aging on liner compared to the carboxylated acrylate emulsion adhesive 5042-184C.
- An acrylamide acrylate emulsion copolymer was compounded with a polyacrylic acid ammonium salt solution to provide adhesive 5121-16.
- This adhesive displayed high initial peel values and similar applied heat aged peel values compared to the acrylamide acrylate emulsion copolymer adhesive 5042-184D.
- the use of the polyacrylic acid solution polymer was found to enhance the peel performance profile of an acrylamide acrylate emulsion copolymer adhesive.
- IPN Interpenetrating Polymer Networks
- IPN systems Two IPN systems were prepared. An acrylamide-containing IPN was formed in a carboxylated acrylate emulsion polymer (4846-82 and 5121-48A, respectively), and a carboxylated IPN was formed in an acrylamide-containing acrylate emulsion polymer (4846-84 and 5121-48B, respectively). An increase in mean particle size during the IPN reactions, conversion, and performance similarities in alternate IPN first and second stage polymerization arrangements is evidence for actual IPN formation.
- IPN emulsion adhesives listed in Table 4 displayed very similar adhesive performance, showing good initial peel and tack values, and low peel build upon applied heat aging.
- Adhesive 4121-48B, an acrylic acid IPN displayed the best peel profile in these comparisons with 30 minutes dwell of 14 oz, 24 hour dwell of 18 oz, one week dwell values of 19 oz, and one week dwell at elevated temperature of 22 oz.
Abstract
Description
TABLE 1 ______________________________________ Comparison Emulsion Copolymer 4886-155 Ingredient Amount (wt-parts) ______________________________________ Monomer Emulsion Butyl acrylate 740.0 Styrene 36.0 Acrylic acid 16.0 Acrylamide 8.0 Triton X-200* 72.0 DI Water** 196.3 Catalyst #1 Sodium Bisulfite 0.8 DI Water 8.0 Catalyst #2 Potassium Persulfate 2.4 DI Water 46.4 Catalyst #3 t-Butyl Hydroperoxide 0.4 DI Water 10.0 Catalyst #4 Sodium Formaldehyde Sulfoxylate 0.2 DI Water 4.0 ______________________________________ *Triton X200 emulsifier is sodium alkyl aryl polyethoxy sulfonate, 28 wt% actives, Union Carbide Corporation, Danbury, CT. **DI Water is deionized water.
TABLE 2 __________________________________________________________________________ Emulsion Polymerization.sup.a Summary Polymer.sup.b Polymer.sup.b Composition Final.sup.c Solids Final.sup.d Viscosity Final Particle.sup.e Size Laboratory Reference Type AMD/AA/STY/BA (wt-%) (cps) pH (nm) __________________________________________________________________________ 5042-154 1 × AA 1.0/2.0/4.5/92.5 58.9 1600 2.3 240 1 × AMD Single Stage 5042-29 1 × AA 0.0/2.0/4.5/93.5 59.8 690 2.2 250 Single Stage 5042-89 1 × AMD 1.0/0.0/4.5/94.5 58.9 1650 2.3 250 Single Stage 5121-8 2 × AA 0.0/4.0/4.5/91.5 57.9 700 2.6 240 Single Stage 5121-10 2 × AMD 2.0/0.0/4.5/93.5 55.9 2850 2.7 270 Single Stage 4864-82 Two Stage IPN.sup.f 1) 0.0/4.0/4.5/91.5 58.0 490 2.1 290.sup.g 2) 2.0/0.0/4.5/93.5 4864-84 Two Stage IPN.sup.f 1) 2.0/0.0/4.5/93.5 54.7 670 2.0 310.sup.g 2) 0.0/4.0/4.5/91.5 __________________________________________________________________________ Footnotes to Table 2 .sup.a) All single stage emulsion polymerizations were conducted in deionized water with preemulsified monomer in deionized water containing 9% Triton X200 surfactant. Polymerizations were initiated with 21.4 grams of monomer emulsion in 230 grams deionized water with a sodium bisulfite potassium persulfate initiator system. Reactions were carried out at 80° C. with delayed monomer emulsion and potassium persulfate solution additions over a three hour period. .sup.b) AMD = Acrylamide, AA = Acrylic Acid, STY Styrene, BA = nButyl Acrylate Polymer composition in monomer weight percent .sup.c) Non-volatile weight percent .sup.d) Brookfield RVF viscosity at 20 rpm, 25° C. .sup.e) Unimodal distribution means obtained on a Coulter Model N4 particle size analyzer. .sup.f) Interpenetrating emulsion polymers were prepared using equal weights of seed emulsion (51218 & 512110) dry polymer and interpenetratin second stage monomers. Initial IPN reaction conditions were adjusted to represent the continuous feed reaction (5042154) at 50% delayed monomer feed reacted The monomer emulsion was added to the first stage emulsion polymer, mixed for 30 minutes, and reacted in two portions. The resulting overall monomer and surfactant compositions for the acrylamide IPN (486482), acrylic acid IPN (486484), and continuous polymerization (5042154) are identical. Experimental details can be found in laboratory notebook 4864. .sup.g) The 40 and 50 nm increase in mean particle size for interpenetrating polymers 486482 and 486484 over the seed latices 51218 and 512110 is evidence of interpenetrating polymer formation. Particle volume increases are about 70% of theoretical.
TABLE 3 __________________________________________________________________________ Compounding Summary Deionized Strodex.sup.g Colloids Aqua.sup.h Laboratory Carboxyl Polymer Source Amide Polymer Source Water SEK-50 679 Ammonia Reference (gram) (gram) (gram) (gram) (gram) (gram) __________________________________________________________________________ 5042-184A Acrylic Acid-Acrylamide 20.0 3.5 0.3 1.5 Containing Acrylic Emulsion Copolymer 5042-154 150.0 5042-184C Acrylic Acid Containing None 0.0 3.6 0.3 1.5 Acrylic Emulsion Polymer 5042-29 150.0 5121-17 Acrylic Acid Containing Polyacrylamide 5% 0.0 3.6 0.3 1.5 Acrylic Emulsion Polymer Aqueous Solution 5042-29 18.0 150.0 5042-184D None Acrylamide Containing 0.0 3.6 0.3 1.5 Acrylic Emulsion Polymer 5042-89 150.0 5121-16 Polyacrylic Acid 5% Acrylamide Containing 0.0 3.5 0.3 1.5 Ammoniated Aqueous Acrylic Emulsion Polymer Solution 5042-89 36.0 150.0 5121-18A Acrylic Acid (2×) None 10.0 3.6 0.3 1.0 Containing Acrylic Emulsion Polymer 5121-8 150.0 5121-18B None Acrylamide (2×) 0.0 3.6 0.3 1.0 Containing Acrylic Emulsion Polymer 5121-10 150.0 5121-18C Acrylic Acid (2×) Acrylamide (2× ) 0.0 3.6 0.3 1.0 Containing Acrylic Containing Acrylic Emulsion Polymer Emulsion Polymer 5121-8 5121-10 75.0 75.0 5121-48A Seed Polymer Acrylic Interpenetrating 12.0 2.0 0.2 2.0 Acid Containing Acrylamide Containing Emulsion Polymer Acrylic Emulsion 5121-8 Polymer (converted) 4864-82 100.0 5121-48B Interpenetrating Seed Polymer Acrylamide 6.0 2.0 0.2 2.0 Acrylic Acid Containing Containing Acrylate Acrylic Emulsion Polymer Emulsion Polymer 4864-84 5121-10 100.0 (converted) __________________________________________________________________________ .sup.a) 2.0 wt% dry phosphate surfactant on dry emulsion polymer level. .sup.b) All emulsions were basified with 14% aqua ammonia until an increase in viscosity was obtained.
TABLE 4 __________________________________________________________________________ Adhesion Performance Summary.sup.a Initial Film and (Aged Film) Properties.sup.b Polyken Shear Laboratory Polymer 180° Peel (lbs/in) Dwell Time Loop Tack Tack 1" × 1/2" × 1 kg Reference Architecture 30 min. 24 Hr. Week Week 70° C. (lbs/in) (gram) (hrs) __________________________________________________________________________ 5042-184A AA/AMD Emulsion 5.6 (3.1) 7.4 (12.2) 11.4 27.3 0.9 (0.6) 200 (300) 10.4 C (21.1 C) Copolymer 5121-18A AA ×2 Emulsion 8.3 (8.0) 9.6 (15.4) 26.5 35.0 1.2 (0.5) 150 (260) 34.5 D (14.0 C) Polymer 5121-18B AMD ×2 Emulsion 1.6 (1.4) 2.0 (2.1) 12.4 20.0 0.8 (0.6) 210 (240) 1.1 A (0.8 A) Polymer 5121-18C AA ×2 Emulsion 4.5 (5.5) 7.4 (8.2) 14.0 21.0 0.8 (1.0) 170 (310) 15.4 (22.1 C) AMD ×2 Emulsion 1:1 Polymer Blend 5042-184C AA Emulsion Polymer 13.4 (13.4) 12.2 (17.6) 18.9 33.4 1.2 (0.9) 220 (370) 3.1 C (2.5 C) 5121-17 AA Emulsion Polymer 13.0 (0.7) 11.6 (1.2) 21.4 29.6 0.7 (1.1) 155 (310) 3.8 C (1.3) AMD Aqueous Polymer Blend 5042-184D AMD Emulsion Polymer 2.6 (1.5) 1.0 (1.4) 3.1 25.0 1.0 (1.3) 250 (310) 2.3 C (2.3 C) 5121-16 AMD Emulsion Polymer 6.2 (2.9) 4.6 (3.7) 16.0 22.2 0.9 (0.7) 90 (280) 0.8 C (1.6 C) AA Aqueous Polymer Blend 5121-48A AMD IPN Emulsion 9.4 (3.0) 15.1 (6.4) 16.1 24.8 1.0 (0.7) 310 (250) 10.7 D (24.6 PD) Polymer 5121-48B AA IPN Emulsion Polymer 14.2 (3.8) 18.5 (10.9) 19.2 21.8 1.1 (1.1) 270 (210) 8.6 D (11.4 __________________________________________________________________________ PD) Footnotes to Table 4 .sup.a) Adhesive evaluations were conducted with 1.0 ± 0.1 mil dry adhesive films transfer coated from H.P. Smith 8024 release liner to 2 mi polyester film. All testing was conducted off stainless steel. .sup.b) Peel tests were conducted under PSTC1 conditions. Heat aging was conducted at 70° C. (158° F.) in forced air ovens for one week. Data for films heat aged on liner prior to adhesive testing is in parenthesis. All heat aged films and laminates were reequilibrated to 70° F. 50% relative humidity for one day prior to testing.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4321175A (en) * | 1978-12-16 | 1982-03-23 | Bayer Aktiengesellschaft | Copolymer dispersions |
US4529772A (en) * | 1983-05-27 | 1985-07-16 | Basf Aktiengesellschaft | Contact adhesive dispersions for the production of self-adhesive articles, for example those having a polyolefinic base |
US4540739A (en) * | 1984-04-10 | 1985-09-10 | Polysar Limited | Adhesive polymer latex |
US4616057A (en) * | 1985-07-10 | 1986-10-07 | Sun Chemical Corporation | Polymer emulsion containing an interpenetrating polymer network |
US4983656A (en) * | 1988-03-14 | 1991-01-08 | Japan Synthetic Rubber Co., Ltd. | Aqueous pressure-sensitive adhesive |
US5025062A (en) * | 1988-03-24 | 1991-06-18 | Basf Aktiengesellschaft | Coating materials based on synthetic resin |
-
1993
- 1993-12-21 US US08/171,196 patent/US5416134A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4321175A (en) * | 1978-12-16 | 1982-03-23 | Bayer Aktiengesellschaft | Copolymer dispersions |
US4529772A (en) * | 1983-05-27 | 1985-07-16 | Basf Aktiengesellschaft | Contact adhesive dispersions for the production of self-adhesive articles, for example those having a polyolefinic base |
US4540739A (en) * | 1984-04-10 | 1985-09-10 | Polysar Limited | Adhesive polymer latex |
US4616057A (en) * | 1985-07-10 | 1986-10-07 | Sun Chemical Corporation | Polymer emulsion containing an interpenetrating polymer network |
US4983656A (en) * | 1988-03-14 | 1991-01-08 | Japan Synthetic Rubber Co., Ltd. | Aqueous pressure-sensitive adhesive |
US5025062A (en) * | 1988-03-24 | 1991-06-18 | Basf Aktiengesellschaft | Coating materials based on synthetic resin |
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